Sciencemadness Discussion Board

Hydroxylamine NH2OH Uses (and Production)

chemoleo - 27-4-2004 at 17:12

Well I have a batch of hydroxylamine sulphate lying about - about 500 g, from a photographys supplier.
I wondered what kind of experiments I could perform with it?

This is what I came up with:

It reacts with ketones/aldehydes to for the respective oximes, i.e.
acetone + NH2OH --> (CH3)2C=NOH

which can be crystallised out in cold water.

Then, one can make nitrous oxide, N2O with it :)

2HONH2 + 4CuO = 2Cu2O + N2O + 3H2O

Very neat method I think, one gets valuable Cu2O and N2O, too!!

Also, there is another one:
R-COOR' + H-NHOH = R'OH + R CO'NH'OH

Meaning that any carboxylic acid ester such as ethyl acetate will react with it, forming a hydroxamic acid.
Also, this produces coloured complexes with Fe3+.

I think there are many more interesting reactions, if you are aware of any please post away!!

[Edited on 22-2-2005 by chemoleo]

I am a fish - 28-4-2004 at 00:15

I expect hydroxylamine nitrate would be fairly interesting. :D

[Edited on 28-4-2004 by I am a fish]

Organikum - 28-4-2004 at 01:42

You can use for a reductive amination - phenylacetylcarbinol to phenylpropanolamine via the oxime.
This forms an interesting oxazoline compound when reacted with KOCN as I was told......

Phenylacetylcarbinol is made by bakers yeast/benzaldehyde - should be not to hard for ya I guess.
(Neuberg/Hirsch 1921)

madscientist - 28-4-2004 at 02:13

What exactly is phenylacetylcarbinol?

Organikum - 28-4-2004 at 02:35

CAS 90-63-1 (1-hydroxy-1-phenyl-2-propanone)

Formula: C9H10 O2
Composition: C, 71.98; H, 6.71; O, 21.31
Mol. Weight: 150.1745
Exact Mass: 150.06808

1-hydroxy-1-phenylacetone, aka Acetylphenylcarbinol, boils at 205-7° C at atmospheric pressure, 135-7° C at 24 mm Hg, 140-5° C at 11 mm Hg and 66° C at .2 mm Hg It's miscible with most organic solvents.

C6H5CHOHCHOCH3
1-hydroxy-1-phenyl-2-propanone
1-hydroxy-1-phenylpropanone
1-phenylpropan-1-ol-2-on (phenylpropanolon) -> old german
phenylpropanolone
1-phenyl-2-ketoalcohol-(1)
1-phenyl-propanol-1-one-2
PAC
Acetylphenylcarbinol
phenylacetyl carbinol
1-phenylpropan-1-ol-2-one
1-hydroxy-1-phenylacetone
1-phenyl-1-hydroxyacetone
Benzacetoin (german)

Funny:
The mostly referred form is laevo-phenylacetylcarbinol aka
l-phenylacetylcarbinol aka
l-PAC aka
L-PAC aka
R-PAC (thats a good one hey!)
because of:
(R)1-hydroxy-1-phenyl-2-propanone is correct for laevo-phenylacetylcarbinol.

Even more funny is that phenylacetylcarbinol is WRONG as this describes an isomer - but as Neuberg and Hirsch who discovered the stuff made this mistake in their first publications (corrected it lateron) the name is still used.

Do you now know why I HATE chemists?

:mad:

chemoleo - 28-4-2004 at 05:47

Well of course, the hydroxylamine nitrate/perchlorate are things to try - they have a large oxygen excess, so I wouldn't try it without something combustible.

Anyway, I seem to recall that there are some reactions on the phenylgroup, with hydroxylamine. Does anyone know more?

Also, what can one do with oximes?
Reductive hydrogenation, to what? Amines?

Kaboom, we need your input ! :)

PS Org, so what is the phenylcarbinol used for?

[Edited on 28-4-2004 by chemoleo]

phenylacetyl carbinol

Hjalmar_Poelzig - 28-4-2004 at 06:24

phenylacetyl carbinol is a precursor for both norephedrine (aka phenylpropanolamine) and ephedrine.

For the first the oxime is made using NH2OH, followed by reduction to the amine.

For the second the ketimine made in situ from methylamine and PAC is reduced to the subst. methylamine.

chemoleo - 29-4-2004 at 15:37

I just had this thought - H2NOH forms oximes with aldehydes and ketones, as we all know.
However, what if we mix hydroxylamine and formaldehyde?
We will get H2C=NOH, which presumably will polymerise in a certain fashion. Now the question is, it will polymerise to what?
In the analogous sitation, ammonia NH3 and formaldehyde CH2O produce hexamethylenetetraamine, which we all know, and it's applications thereof (hint hint ;)) - so what will happen with hydroxylamine?

Lets bring out the organic chemists!!!

Organic Chemistry

Turel - 30-4-2004 at 06:33

Organikum: That oxazoline is indeed interesting, as I'm sure you know. I've been interested in 4-MAR for a few years.

madscientist chemoleo: levo-phenylacetylcarbinol (L-PAC) is the biochemical precursor to PPA and ephedrine, from which plants produce these two compounds in nature. Microorganism exploitation leads to the same result in a petri dish or larger reactor.

Methylene hydroxylimine could polymerize in two different ways. It could repeating chains of [-CH2N(OH)-]n where the methylene carbon and nitrogen form the linkages. In my opinion this rather low stability bonding would likely form small rings able to be stbilized by resonance/tautomerization of the hydroxyl to a nitroso function.

The other method would form longer chains of compounds of repeating [-CH2N(H)O-]n functions where the methylene carbon forms bond with oxygen and nitrogen. This will also be prone to hydrolysis as the first is.

Theoretic - 20-10-2004 at 07:12

Maybe reacting formic acid with hydroxylamine will give you fulminic acid? :o

NH2OH + HCOOH => HCOHNOH
HCOHNOH => HNCO + H2O

Edit: Hydroxylamine, I think, would react with formaldehyde to from a hexamethylenetetramine type compound, except that every nitrogen will have a coordination covalent bond (donation) to an oxygen atom. From this compound, HMX or RDX could be made which has either a nitrate group attached to the nitrogen atoms of the ring (instead of a nitro group), or every ring nitrogen atom will have an oxygen attached to it. This tri-N-oxo RDX or tetra-N-oxo HMX will have perfect OB and will presumably be more powerful.

[Edited on 21-10-2004 by Theoretic]

BromicAcid - 20-10-2004 at 15:05

You could make sodium or silver hyponitrite (Ag2O2N2). The prep in Am. Chem. Soc. Oct. 1924, pps. <2175 involves the use of hydroxyl amine as one of the starting agents for this compound. I only have a paragraph of the article photocopied (the last paragraph, copied it when I was copying the article following it, and whenever I saw that last paragraph I thought of this thread.).

Mendeleev - 27-11-2004 at 01:09

Does anyone have a synthesis for hydroxylamine? I searched the net, and all I found directly relating to hydroxylamine synthesis was this http://www.korozja.pl/131_01_03.pdf . Not that you need to synthesize it, it's pretty cheap at around $25-50 per kilogram, but it would be good to know.

Edit: Nevermind, I found this from Rhodium:


Preparation of Hydroxylamine hydrochloride

40g potassium nitrite (KNO2) and 50g potassium acetate (CH3COOK) are dissolved in 100ml ice water. 750g finely crushed ice is added. Into this solution a stream of sulfur dioxide (SO2) is bubbled until the solution smells of SO2. The temperature must be kept below 0°C through the whole reaction. The salt of K2[HON(SO3)2] separates and is filtered off and washed with ice water. The salt is dissolved in 500ml 0.5 M HCl and boiled for two hours. Still boiling a solution of Barium chloride (BaCl2) is added as long as barium sulfate (BaSO4) precipitates (maybe CaCl2 will do instead). The BaSO4 is filtered off and the clear filtrate is evaporated to dryness. The residue consists of Potassium Chloride (KCl) and NH2OH*HCl. Anhydrous ethanol(EtOH) is used for extraction of the Hydroxylammonium chloride, the KCl remains undissolved. The EtOH is evaporated on a water bath and the product can be recrystallised from water (mp 151°C).

[Edited on 27-11-2004 by Mendeleev]

BromicAcid - 21-2-2005 at 19:56

From:
MICROWAVE SPECTRUM OF FORMALDOXIME
M. G. Krishna Pillai;
J. Phys. Chem.; 1962; 66(1); 179-180.

Quote:
"Formaldoxime was prepared by mixing an aqueous solution of formaldehyde with a solution of hydroxylamine hydrochloride to which sufficent sodium carbonate had been added to liberate the hydroxylamine(2). From the mixture formaldoxime was extracted with ether. The polymer of formaldoxime, obtained by the evaporation of the etheral solution, gives our the monomer when heated."




(2) W.R. Dustan and A.L. Bossi, J. Chem. Soc., 73, 353 (1898)

Picture of formaldoxime attached :)

formaloxime.jpg - 10kB

neutrino - 21-2-2005 at 20:04

Excuse my lack of ochem knowledge, but could this be mixed with nitric acid to form RDX? Maybe it could be nitrated into some other interesting explosive?

Formaldoxime and potential nitrates?

chemoleo - 21-2-2005 at 20:16

Of course, that's the whole idea. I recently tried this experiment, and the solution of hydroxylamine and CH2O heats up considerably. Until recently I didn't know the products, thanks to Bromic and myself for having the ingenious idea that the product might be called 'formalDoxime' (rather than formaloxime which yielded no search hits);)
Anyway, theoretically there should be a trinitrate, practially probably only a dinitrate exists (or diperchlorate ;))
This is something that ought to be tested. It is likely to be more powerful than hexamethylene tetramine dinitrate (due to a distinctly better OB)

However, I don't think that an analogue to hexogen/RDX can be formed, because there is no free hydrogen attached to the nitrogen. I.e. hexogen/RDX is a nitramine, i.e. a nitro-amine, which is not possible in the case of formaldoxime.

[Edited on 22-2-2005 by chemoleo]

Caffinehog - 16-3-2005 at 21:21

Uses of hydroxylamine..... How about converting ketones to amides?
Mix it with a ketone. This forms the oxime. Then add a medium strength acid, like phosphoric acid, and warm it. This causes the Beckman rearrangement. You get an amide, with primarily the larger organic group on the nitrogen. Acetone ----> N-methyl acetamide. Acetophenone ---->acetanilide.
Heat it too much or/and add to strong an acid, and you will hydrolyze it to the corresponding carboxylic acid and amine. For example, acetophenone + hydroxylamine + heat +HCl ----> acetic acid + aniline

Theoretic - 17-3-2005 at 13:43

It won't be a nitramine, this HMX analog, but it will be an oxamine, since the acid would react with the hydrogen atom of the hydroxyl group attached to the nitrogen to leave the nitro group in its place. A whole new class of explosives, oxamines! :P

chemoleo - 17-3-2005 at 16:07

Caffinehog, that's very interesting. An easy route to amides - with OTC hydroxylamine - nice. Here's some more detail on the Beckmann rearrangement. Although they actually mention conc H2SO4. I guess it depends on the type of oxime.
I was wondering, can the oxime be reduced easily to the respective amine? I imagine this needs rather strong reducing agents, such as LiAlH4 etc. Or electrolysis?
I.e. according to
CH3COCH3 + NH2OH --> CH3C(=NOH)CH3 --> CH3HC(NH2)CH3 (2 propylamine)?

Theoretic, as far as I know formaldoxim is hydrolysed back to hydroxylamine and CH2O in the presence of acids. So this wouldn't work.
Are you talking of a NITRATE group on a nitrogen? I.e. R2N-O-NO2? I don't even know whether that exists.

Theoretic - 19-3-2005 at 12:13

If you use a direct nitrating agent (a compound of the NO2+ ion) like NO2HSO4, hydrolysis could be avoided, not so if you use nitrating acid (H2SO4/HNO3). NO2HSO4 can be made from concentrated HNO3 and sulfur trioxide, obtainable by decomposing ferric sulfate.
And yes, I'm talking about R2N-O-NO2. What about a nitrate group on a nitrogen? N2O3 and N2O5 do exist, and they have it.

Axt - 1-2-2006 at 16:22

I'm attaching an article which supposedly gives the synthesis of NH2OH.HCl by refluxing HCl with nitromethane.

<a href="http://xfiles.ft100.net/images/nm-hcl-hydroxylamine.pdf">Journal f. prak. Chemie, Vol 21, 1880, page 129</a>

Can a german speaker please look at that and give the specifics of the reaction (quantities, reflux time, extraction etc.). If its in there ... somewhere.

More random NH2OH articles I have:

http://scibooks.ft100.net/images/hydroxylamine.zip

S.C. Wack - 2-2-2006 at 03:21

Funny that you bring this up, as just 48 hours ago I was reading this:

Attachment: iec_31_118_1939.pdf (433kB)
This file has been downloaded 1368 times


chemoleo - 19-2-2006 at 18:33

Interesting references. I always love these old gems, with obscure structures, where things such as the structure of hydroxylamine weren't entirely elucidated, or at least where there's some debate. Still a frontier of science of sorts.

Anyway, here's the translation for the
Preparation of hydroxylamine from nitromethane:
25-28 gram of nitromethane was heated with twice the volume of HCl (presumably 37% although this isn't specified) in a glass (test?) tube that was melted and sealed (similar to an ampoule), and heated to 100 deg C. After cooling the tube (no mention is made as to how long, but see the below), where higher pressure only occurred intermittendly (in other words, the glass container was able to resist the probably weak pressure), hydroxylamine hydrochloride crystallised as glorious, almost inch-long crystals (where the remaining solution presumably consists of HCl, formic acid and H2O). Remaining free HCl was removed by heating them for a prolonged time on a waterbatch, and by a single recrystallisation step. Yield is 18-20 g, and compared to the Loss's procedure, it is faster and yields a cleaner product. It makes no mention of refluxing this mix - might be difficult with the HCl present, but I don't know.


Sounds like a good method, the only drawback being a pressure container. But by the sound of it, a glass ampule is enough, so a strongly stoppered pyrex flask in a 100 deg C bath should be fine, right?

Also, it mentions that the hydroxylamine HCl can be reacted with cyanamide to form oxyguanidin hydrochloride, CN3H5O:HCl. What precisely is this? Anyone knows?

Cyanamide sounds like an extremely versatile compound....!

garage chemist - 20-2-2006 at 12:34

I tried something out today: In a thread on production of N2O, it was mentioned that extremely pure N2O is obtained by combining solutions of a hydroxylamine salt and a nitrite.
It's only stupid that all sources of hydroxylamine salts are really expensive, at least those that I know. I purchased 25g of the sulfate for some experiments.

I added 1,6g of di-hydroxylamine sulfate (0,01 mol) and 1,4g NaNO2 (0,02 mol) (stochiometric amounts, you see) to a test tube, and added 15ml water. The salts dissolved upon swirling, and gas production started immediately, despite the solution being very cold from endothermic dissolution of the NaNO2.
This was a marked difference to the reaction of an ammonium salt with NaNO2, which takes place only on warming.
The solution continued fizzing, and the gas evolution became stronger and the solution heated up, and as soon as it was mildly warm to the touch, runaway occured and the solution frothed over, it went so fast that I couldn't do anything against it.

So this method produces N2O in good amounts, but temperature control is critical to prevent runaway and only dilute solutions should be used.

Microtek - 21-2-2006 at 05:26

I have tried the HCl + nitromethane reaction in an effort to prepare energetic furazan compounds ( diamino furazan can be made from condensation of glyoxal and hydroxylamine to diaminoglyoxime followed by ring closure with aqueous KOH ).
I refluxed 20 ml NM with ca. 25 ml HCl, 30 % for about 24 hours total ( I let it cool down in the evening as I don't like heating something overnight ). The HCl was ancient ( 10-20 years ) and had a strong yellow coloration, probably from the green PE bottle which it was stored in. Towards the end of the process, I noticed that the mix still separated into two phases ( which it obviously shouldn't if the reaction had gone to conclusion ), so I added a little more acid and in the course of a few hours, it became homogenous.
I then cooled it down, but no crystals appeared. So, I left it sitting there and didn't get around to evaporating a sample for some weeks.
When I did get around to it, I got a reasonable amount of crystals which where soluble in ethanol, strongly reducing and quite hygroscopic. The only crystalline impurity that I can think of is NH4Cl which is almost insoluble in ethanol ( 0.6 g/100 ml at room temp ).
Apart from the long heating period, the only problem seems to be the isolation as hydroxylammonium chloride starts to decompose around 120 C so evaporation to dryness should be done very carefully. I ended up heating it gently until only some 10-20 ml remained, then putting it in a desiccator over a mix of CaCl2 and CaOH.
I contemplated a redox titration to determine the purity, but this is complicated by multiple oxidation products ( N2, N2O, NO, NO2, NO3- ). I tried acidified KMnO4 which I like because it goes all the way to colorless Mn2+. The hydroxylamine turned the KMnO4 soln completely clear without visible gas evolution, so maybe it is safe to assume ( for a rough estimate of purity ) that the hydroxylamine is oxidized all the way to nitrate...

garage chemist - 21-2-2006 at 09:21

I had a look in Hollemann- Wiberg on hydroxylamine, and guess what, the reaction of aqueous sulfuric acid and nitromethane is an industrial method for the production of hydroxylamine sulfate.

Apparently, other nitroalkanes can be used as well, they get converted to the corresponding carboxlic acids and hydroxylamine.

chemoleo - 21-2-2006 at 10:07

That's surprising really, because of the high cost of nitromethane. Isn't the bisulfite/nitrite method for hydroxylamine production way more economical?

Microtek - 21-2-2006 at 12:52

Well, in Ullmann's Encyclopedia of Industrial Chemistry it says that "This process has been used only to a limited
extent because of its cost and the limited availability
of raw materials." about the NM/acid process.
The Raschig process is more important as is the catalytic hydrogenation of NO or nitrates.
But since I can buy NM and not nitrite, the acid/NM method is the one I'm giong with.

Axt - 25-2-2006 at 13:24

Thanks for translation, alternatives, experiances!

Quote:
Originally posted by chemoleo
Also, it mentions that the hydroxylamine HCl can be reacted with cyanamide to form oxyguanidin hydrochloride, CN3H5O:HCl. What precisely is this? Anyone knows?


H2N-C(=NH)-O-NH2 . HCl?

There is mention of (NH2O)2C=NH here,
http://ww1.ft100.net/~64671/xfiles.ft100.net/images/oxylamin...
forget what the actual journal ref this come from, I have so much of this crap on my computer, in german ... again :(

Quote:
Originally posted by Microtek
diamino furazan can be made from condensation of glyoxal and hydroxylamine to diaminoglyoxime


Were you able to do that in good yield in one step? See pg 377 of preceedings <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=5393">here</a>, supposedly you can go all the way to diaminofurazan in one step from glyoxal/NH2OH.HCl/NaOH + "other", but specifics arn't mentioned.

I've isolated glyoxime, then diaminoglyoxime from that, but only in ~20% from glyoxal -> DAG.

[Edited on 25-2-2006 by Axt]

Microtek - 26-2-2006 at 05:55

No, I haven't actually tried that yet as I've only just gotten the hydroxylamine production in place. I plan to follow the modification proposed in "Furazan-based Energetic Ingredients" which I think I got from you at the Crucible.
The modification involves heating an excess of free hydroxylamine to 90 C and then dripping in glyoxal soln while maintaining the mix at 90 C. According to the article I mentioned, yield suffers if temp rises above 90 C which can be difficult to control if mixing the ingredients first and then heating. This should give diaminoglyoxime directly in 64 % yield ( at the 1000 g scale ).

More uses of hydroxylamine

chemoleo - 27-2-2006 at 16:39

I had a look at Axt's article from above. It contains some interesting chemistry, some that even seems doable!

For instance, potassium hydroxylamine disulphate (KO-N(SO3K)2), which is made as described above from sulfite and nitrite, is a useful reagent for the reaction with alkylating agents, for instance dimethylsulphate or, more realistically, halogeno-alkanes.

Alpha-methyl hydroxylamine, CH3-O-NH2
Basic potassium hydroxylamine disulphonate (dissolved in 6% KOH) is mixed with the same molar quantity of dimethylsulphate or methyliodide. The latter disappears within one day, while DMS reacts much faster while heating up. This can be boiled down, and alpha methyl hydroxylamine dipotassium disulphonate CH3-O-N(SO3K)2 crystallised in good yields, which can be recrystallised in slightly ammonia-containing H2O.
To split the N-SO3 bonds, the above salt is boiled in H2SO4, under reflux. I'm not sure if reflux is necessary, but probably topping up with H2O now and then would be good. The end of the reaction is achieved after several hours. (The end is recognised by taking a small aliquot of the solution, adding BaCl2/OH2 to remove extra H2SO4, and nitrite is added, which will react with the hydroxylamine. If H2SO4 is released, then addition of further BaCl2/OH2 will result in further precipitation, which indicates unreacted sulphonic acid. Thus more boiling is required).
Once the reaction is finished, the CH3ONH2:H2SO4 salts are extracted with ethanol, seemingly recrystallisation in ethanol can separate the less soluble neutral salt ((CH3ONH2)2:H2SO4) from the more soluble acidic salt (CH3ONH2:H2SO4).

They summarise this to make this reaction as fast as possible:
1) methylate the potassium hydroxylamine disulphonate in basic solution, as described above.
2) Boil this with H2SO4 or HCl to dryness, while the former is prob better (no HCl fumes), and test for completion of the reaction.
3) Add NaOH to a stoichiometric excess (cooling), and boil and distill. Free methyl hydroxylamine base comes over with the water, and is directely either collected in acid, or simply in a cooled container. Yields, wrt the starting compound, is 80%

Interestingly, the methyl hydroxylamine nitrate, explodes with great force when heated to 300 deg C. The nitrate is well-soluble in absolute ethanol, which may provide a purification technique. Maybe, Axt, that's something you want to try!!!! :)

Alpha, alpha ethylene dihydroxylamine, H2N-O-CH2-CH2-O-NH2)

Again, energetic compounds of this hydroxylamine can be easily seen :)
Here, 1,2 dibromo ethane is required, Br-CH2-CH2-Br. The sulphonate salt from above is reacted with it, in a 2:1 proportion, as described with the methyliodide above. This forms the tetrasulphonate, similar to the reaction above, which precipitates/crystallises from solution due to its low solubility:

(KSO3)2N-O-CH2-CH2-O-N(SO3K)2

This is digested with H2SO4, under boiling and testing for the end of the reaction as described above. The free based distills at 203 deg C.

Next to making the nitrate salts, I wonder how good a substrate these hydroxylamines are for peroxidation...? Similar to the 'amine peroxide' thread.


Other than alkylhalides, the initial hydroxylamine sulphonate also reacts with cyanogene bromide or iodide. Sadly this is not an easy substnace, nor safe. This then forms the imine sulphonate, (KSO3-N-O)2C=NH. However, this does not form the (NH2O)2C=NH, which Axt mentioned, even though boiling this with acid should theoretically get this.


Altogether, I think this may open up potential for a whole series of compounds, given the right starting compounds (alkylhalides).

Who's going to make some methyl-hydroxylamine nitrate? :P

[Edited on 28-2-2006 by chemoleo]

JohnWW - 1-3-2006 at 08:30

Quote:
Originally posted by Axt
I'm attaching an article which supposedly gives the synthesis of NH2OH.HCl by refluxing HCl with nitromethane.
<a href="http://xfiles.ft100.net/images/nm-hcl-hydroxylamine.pdf">Journal f. prak. Chemie, Vol 21, 1880, page 129</a>

Can a german speaker please look at that and give the specifics of the reaction (quantities, reflux time, extraction etc.). If its in there ... somewhere.

More random NH2OH articles I have:
http://scibooks.ft100.net/images/hydroxylamine.zip


Those links are broken.

solo - 1-3-2006 at 09:48

Try to secure them here........solo

http://rapidshare.de/files/14438117/nm-hcl-hydroxylamine.pdf...

http://rapidshare.de/files/14438496/hydroxylamine.zip.html

gsd - 1-3-2006 at 10:22

No. The links are alright.

I could download both files.

JohnWW - 3-3-2006 at 17:08

Thanks for the renewed links, Solo.

Axt - 3-3-2006 at 22:45

For some reason the links seem to work for some but not others.

I remember where that "oxylamine" article come from, it was referenced to in PATR2700 under the entry ethylenedioxyamine. Making it Ber 53, 1489 (1920).

PATR2700 gives no actual figues but a few properties, the dinitrate detonates when heated over its melting point, and the diperchlorate is responsible for killing the two chemists working with it :) they refer to it as a "sensitive material".

Apart from the salts and possible peroxides, complexes are likely and chloramines may be possible as well. It would be interesting to try the same peroxide/complex/salts/chloramine with diaminofurazan as is possible with the alkyl amines.

The O-methylhydroxylamine or methyloxyamine is patented as rocket fuel as replacement for hydrazine US3117415, though the only sythesis reported is that translated by Chemoleo.

gilaneh - 11-12-2006 at 01:03

i have a question. do you know anything about role of pyruvic acid in biosynthesis of l-PAC?

unionised - 11-12-2006 at 03:51

Yes, I know it's not clearly on-topic.

guy - 26-2-2007 at 13:09

Wikipedia says nitrATE and bisulfite will form hydroxylamine. Im pretty sure NO3- will reduce to NO2- and then will form hydroxylamido-N,N-disulfate anion. Heat for 1 hr at 100oC in acid to get hydroxylamine salt.

Sounds easy and I might try it. Any suggestions on what I should expect? For example, how will I know when the potassium hydroxylamido-N,N-disulfate has formed?

guy - 2-3-2007 at 19:33

Does bisulfite reduce potassium nitrate to nitrite?

I mixed some nitrate with Iron Out(sodium dithionite and sodium bisulfite) and some HCl in ice water. And nothing seemed to happen except SO2 gas coming off. I thought the nitrate would oxidize the the SO2 quickly.

Nicodem - 3-3-2007 at 00:54

Don't trust Wikipedia on such things. Bisulphites are in my opinion unable to reduce the nitrate anion. In acidic enough conditions HNO3 should oxidize H2SO3 (or SO2). However this would produce NO2 and ultimately NO, but not hydroxylamine.
I think some Wiki author made a very common mistake of translating the old term "hydrosulfite" to bisulphite when it actually means dithionite. I assume this since sodium dithionite might perhaps be an appropriate reagent for the nitrate->hydroxylamine reduction in basic enough media, but I'm not familiar with inorganic chemistry so rather check Gmelin for the reference by yourself.

guy - 3-3-2007 at 13:21

I actually wrote down the equation for the reaction of nitrate with bisulfite and it turnes out that H+ does not play any role! So it would only react extremely slow in aqueous but it would work when the two are heated together (as I just read in the ionic nitrites thread).

Hydroxylamine HCL synthesis from nitromethane+acetic acid+HCL

overunity33 - 26-1-2010 at 00:04

I found this description somewhere :

Quote:

400 mls nitromethane, 600 mls Acetic acid and 600 mls HCL are heated to just below reflux and held there for 2 hours then refluxed for 12 hours. The solution is reduced to half gone the cooled in fridge overnight and filtered.


I don't understand the mechanism behind the reaction, can anyone explain it? Yields are reported to be 100%+ somehow. What can the resulting product be washed/recrystallized with to increase purity? I assume this reaction utilizes glacial acetic acid and muratic acid, anyone have insight?

Nicodem - 26-1-2010 at 08:10

"I found this description somewhere" does not say where you found it! :mad:

The only way to know more about the mechanism would be to check the original paper where the reaction was described. Sometimes the authors propose the mechanism and give supporting evidence or further reference. So why don't you check the literature? Two references where already given in our hydroxylamine thread, so half of the work is already done. All there is for you is a trip to the library.

The interpretation of the reaction by using the "likely mechanism" approach as though to students would give a tautomerization-elimination-hydrolysis route. The mechanism for the tautomerization of nitromethane is described in many schoolbooks, the mechanism of the elimination might or might not first involve the protonation of aci-nitromethane, while the hydrolysis of fulminic acid is rapid at such conditions and is well known since the year 1882 (J. Chem. Educ., 77, 851-857). I'm not going to waste time drawing such a mechanism proposal, but in short version and skipping a whole lot of intermediates and all the arrow pushing:

MeNO2_HONH2.gif - 3kB

overunity33 - 26-1-2010 at 18:00

I wrote about this in another thread because I couldn't find this one. I found a method somewhere else but I could not find literature or any other type of reference.

(double post removed)

Edit by Nicodem: I merged your thread with this one. Next time do not double post, particularly not if you have already been receiving answers to your original post! And it is "HCl" as for hydrochloric acid, and not "HCL" as you keep mistaking.

[Edited on 27/1/2010 by Nicodem]

franklyn - 21-5-2010 at 06:35

Hydroxylamine has been considered as a monopropellant a possibility is the
borane salt , 3 HONH2•BH3 => B2O3 + BN + N2 + 9 H2

Related threads _
This reference on Hydroxylamine produced by reduction of HNO3 by electrolysis
http://www.sciencemadness.org/talk/viewthread.php?tid=1716#p...
is complimented by the detailed mention in the lower image posted below specifically
citing the method outlined on page 32 of The Manufacture of Chemicals by Electrolysis
from here _ http://www.sciencemadness.org/talk/viewthread.php?tid=13871#...

Hydroxylamine from primary nitroalkanes.gif - 11kB Hydroxylamine from HNO3 by electrolysisi.gif - 123kB

franklyn - 13-1-2011 at 23:56

Many thanks to kmno4 for alerting that Journal of Energetic Materials is for now freely accessible.
http://www.sciencemadness.org/talk/viewthread.php?tid=3724&a...

These interesting amine bases and their salts related by chemoleo here
http://www.sciencemadness.org/talk/viewthread.php?tid=1928&a...
methyl hydroxylamine nitrate, and ethylene dihydroxylamine, are not " hydroxyl " amines
once that has been replaced by an organic functional group. The nomenclature is then
Oxyamine. These analogs of methylene diamine and ethylene diamine contain oxygen bridging
the carbon and nitrogen. The adduct of Methylene (bis)Oxyamine CH2(-O-NH2)2 with
Nitramine or Dinitrourea is unresearched.
CH2(-O-NH2)2 •2 H2NNO2 => CO + 5 H2O + 3 N2
CH2(-O-NH2)2 • (HNNO2)2CO => CO2 + CO + 4 H2O + 3 N2

Synthesis and characterization of Methylene (bis)Oxyamine CH2(-O-NH2)2 salts
http://www.informaworld.com/smpp/ftinterface~content=a752776...

Synthesis and Characterization of Energetic 1,2-(bis)Oxyamino Ethane Salts
http://onlinelibrary.wiley.com/doi/10.1002/prep.200600027/ab...

High Density Energetic Mono- or (bis)Oxy-5-Nitro imino tetrazoles.pdf ( copy both lines below together )
http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Predn%E1%9Aka%203/Doplnkov%E9%20%9Atudijn%E9%20materi %E1ly/High-Density%20Energetic%20Mono-%20or%20Bis(Oxy)-5-Nitroiminotetrazoles.pdf
References from the bibliograpphy 15, 16 , 17
[15]
a) C. S. McDowell, M.W. Barnes, U. S. Patent 3709920, 1973;
b) C. S. McDowell, C. Merrill, U. S. Patent 3714200, 1973;
c) C. S. McDowell, C. Merrill, U. S. Patent 3714199, 1973;
d) Russ. J. Org. Chem. 2004, 40, 124 – 126
D. V. Davydov, I. P. Beletskaya,
http://www.springerlink.com/content/r260w7181k546243
Available from Madhatter's archive

[16] ( these are the first 2 links cited above )
a) J. Energ. Mater. 2001, 19, 277 – 303;
K. Tollison, G. Drake, T. Hawkins, A. Brand, M. McKay, I.Ismail, C. Merrill,
b) Propellants Explos. Pyrotech. 2006, 31, 196 – 204.
T. Hawkins, L. Hall, K. Tollison, A. Brand, M. McKay,
( had been posted as a download from rapidshare )

[17] Synthesis of 12: ( 1,2-(bis)Oxyamino Ethane )
J. Org. Chem. 1984, 49, 4487 – 4494.
D.W. Dixon, R. H. Weiss,

related thread
http://www.sciencemadness.org/talk/viewthread.php?tid=13174

.

Random - 14-1-2011 at 01:09

http://www.erowid.org/archive/rhodium/chemistry/hydroxylamin...

Check this method, maybe it works. I think I saw that method on illumina-chemie.de also, but it gave very low yield, maybe they did not do it right.

I could try this method on test tube scale, just I need to substitute potassium salts for sodium. Would that work then? I only have potassium metabisulfite.

By the way, I read on wikipedia that it is explosive, is it? I dont want to prepare compounds that will blow up me.

MeSynth - 12-8-2011 at 19:16

Quote: Originally posted by Organikum  


Even more funny is that phenylacetylcarbinol is WRONG as this describes an isomer - but as Neuberg and Hirsch who discovered the stuff made this mistake in their first publications (corrected it lateron) the name is still used.



weird

[Edited on 13-8-2011 by MeSynth]

poopyMcgee - 2-9-2011 at 04:01

Thought i would chime in!

Reagents
150 ml 36% HCL
150 ml Glacial Acetic Acid (LG)
100 ml Nitromethane (Hobby Grade, apparently 99%)

Method
HCL, GAA and NM added to 1L flask and manually mixed. Mixture was heated, without mixing, to 60C and held for 30 minutes and then gradually increased to 90C and held there for 2 hours. Mixture took on yellow translucent appearance. Gentle reflux was achieved within 1L flask, no vapor was entering condenser. After 2 hours temperature was increased to 103C to achieve reflux and held for a 12 hour period. Mixture was cooled and left to stand for 24 hours. A white crystalline mass was achieved, flask was subsequently decanted, crystals agitated, removed and dried with a weight of 25 g. Decanted liquid was then reduced to half it volume, cooled and again decanted another 48g of crystalline material was recovered.




AndersHoveland - 16-2-2012 at 17:54

Quote:
Preparation of Hydroxylamine hydrochloride by reduction of nitrite, using sulfur dioxide
40g potassium nitrite (KNO2) and 50g potassium acetate (CH3COOK) are dissolved in 100ml ice water. 750g finely crushed ice is added. Into this solution a stream of sulfur dioxide (SO2) is bubbled until the solution smells of SO2. The temperature must be kept below 0°C through the whole reaction. The salt of K2[HON(SO3)2] separates and is filtered off and washed with ice water. The salt is dissolved in 500ml 0.5 M HCl and boiled for two hours. Still boiling a solution of Barium chloride (BaCl2) is added as long as barium sulfate (BaSO4) precipitates ( CaCl2 may possibly work instead). The BaSO4 is filtered off and the clear filtrate is evaporated to dryness. The residue consists of Potassium Chloride (KCl) and NH2OH*HCl. Anhydrous ethanol(EtOH) is used for extraction of the Hydroxylammonium chloride, the KCl remains undissolved. The EtOH is evaporated on a water bath and the product can be recrystallised from water (mp 151°C).

Mix cold saturated solutions containing one molecular proportion of sodium nitrate, and two molecular proportions of acid sodium sulphite, and then adding a saturated solution of potassium chloride to the mixture. After standing for a day, hydroxylamine potassium disulphonate crystallizes out. This is boiled for some hours with water and the solution cooled, when potassium sulphate separates first, and then hydroxylamine sulphate.



Free hydroxylamine is both unstable and very hygroscopic, and relatively volatile (melts at 33 C and boils at 58 C), which is the reason it is normally found in the form of the hydrochloride salt.

If you make separate solutions in ethanol of hydroxylamine hydrochloride and potassium hydroxide, and then mix, you precipitate KCl, which you can filter off, and end up with a fresh solution on NH2OH in ethanol which can be used straight away and is much more stable.


I also had an idea to modify the ketazine process to use make hydroxylamine instead of hydrazine. Not sure if it would work...

Preparation of Hydroxylamine using the oxime process ?
Sodium hypoclorite (bleach) and ammonium hydroxide would react to produce chloramine gas (NH2Cl). This unstable poisonous would then be bubbled into a solution of methylethylketone and sodium ethoxide* dissolved in pure alcohol. The chloramine gas reacts with the methylethylketone and sodium ethoxide to form O-ethyl-methylethyloxime, with a structure CH3CH2ON=C(CH3)CH2CH3.
The byproduct, NaCl, precipitates out at the bottom at this time, since it is not soluble in alcohol. The progress of the reaction can be estimated by the formation of the solid byproduct.

Cool the contents and allow an hour for all the NaCl to settle at the bottom, then decant out the liquid into a separate container, leaving the all solid at the bottom in the first container. The O-ethyl-methylethyloxime then hydrolyzes with a 20% solution of sulfuric acid to form hydroxylamine sulfate. This would mostly precipitate out at the bottom if only a small amount of the acid solution is added.

*(The sodium ethoxide could be prepared by adding solid NaOH pure alcohol. After several hours, the bottom will consist of solid hydrated NaOH, a small layer of water saturated with NaOH will form immediately above, and the top layer will consist of pure alcohol with the associated sodium ethoxide dissolved in it. The top layer would be decanted out. Alternatively, Na2CO3, used to regulate pH for use in pools, and CaO, used as cement lime can be used instead of solid NaOH, 90% concentrated alcohol can then be used )
http://www.sciencemadness.org/talk/viewthread.php?tid=2656&a...
http://www.sciencemadness.org/talk/viewthread.php?tid=17074


Hydroxylamine (and its compounds) may also be of interest for propellents and explosives:
hydroxylamine perchlorate, hygroscopic solid
melting point between 87.5 and 89degC.
Decomposes at 120degC.
Drop height value of only 2cm, meaning very sensitive to impact.
addition of small ammounts of hydroxylamine perchlorate to several propellents could roughly double their burning rates
US 3748199 (1965)



[Edited on 17-2-2012 by AndersHoveland]

Nitroalkanes

Ephoton - 17-2-2012 at 23:38

another use for hydroxylamine would be making nitroalkanes
from aldehydes.



Attachment: Oxidation of Oximes to nitroalkanes.djvu (93kB)
This file has been downloaded 505 times


Waffles SS - 18-2-2012 at 08:24

I have BASF Hydroxyl Ammonium Sulfate and i want to convert it to Chloride salt.I want to use barium chloride solution for this purpose
Unfortunately i cant evaporate solution to get dry Hydroxylammonium chloride by heat, because it will decompose during boiling.I am looking for another simple and safer method.someone can help me?

[Edited on 18-2-2012 by Waffles SS]

bahamuth - 18-2-2012 at 09:10

Quote: Originally posted by Waffles SS  
I have BASF Hydroxyl Ammonium Sulfate and i want to convert it to Chloride salt.I want to use barium chloride solution for this purpose
Unfortunately i cant evaporate solution to get dry Hydroxylammonium chloride by heat, because it will decompose during boiling.I am looking for another simple and safer method.someone can help me?

[Edited on 18-2-2012 by Waffles SS]


Evaporate under vacuum or in a desiccator (or in a vacuum desiccator), or even crystallize it in a beaker covered with a filterpaper to keep out dust, on top of a shelf. Though the latter might not do if the hydroxylamine has a very high affinity for moisture.

Hope this helps:)

Nicodem - 18-2-2012 at 14:39

Quote: Originally posted by AndersHoveland  
I also had an idea to modify the ketazine process to use make hydroxylamine instead of hydrazine. Not sure if it would work...

Preparation of Hydroxylamine using the oxime process ?
Sodium hypoclorite (bleach) and ammonium hydroxide would react to produce chloramine gas (NH2Cl). This unstable poisonous would then be bubbled into a solution of methylethylketone and sodium ethoxide* dissolved in pure alcohol. The chloramine gas reacts with the methylethylketone and sodium ethoxide to form O-ethyl-methylethyloxime, with a structure CH3CH2ON=C(CH3)CH2CH3.
The byproduct, NaCl, precipitates out at the bottom at this time, since it is not soluble in alcohol. The progress of the reaction can be estimated by the formation of the solid byproduct.

Cool the contents and allow an hour for all the NaCl to settle at the bottom, then decant out the liquid into a separate container, leaving the all solid at the bottom in the first container. The O-ethyl-methylethyloxime then hydrolyzes with a 20% solution of sulfuric acid to form hydroxylamine sulfate. This would mostly precipitate out at the bottom if only a small amount of the acid solution is added.

Why do you have this urge to clutter the forum with such nonsense? You were already told several times to limit yourself to referenced ideas. What you wrote above is such a flight of fancy that it deserves no comment, except that you are again trying to endanger the unaware people who might be ignorant enough to follow your advice. At least have the decency to try your bad advices on yourself first.

AJKOER - 9-11-2012 at 10:58

Actually, here is a better route to the poisonous NH2Cl per Wikipedia and my personal experience. To quote (see http://en.wikipedia.org/wiki/NH2Cl ):

"NH2Cl is prepared by the chemical reaction between ammonia and hypochlorous acid[3] under mildly alkaline conditions:

NH3 + HOCl → NH2Cl + H2O

In this reaction HOCl undergoes attack by the nucleophile NH3. At a lower pH, further chlorination occurs."

Note, 'further chlorination' mentioned above by Wiki does not stress the need to avoid the formation of the highly explosive and unstable Nitrogen trichloride, a thick oily yellow chlorine smelling compound, which is sensitive to organic substances, direct sunlight, shock and heat resulting in a deadly detonation. Historically, NCl3's explosions have costs limbs, eyes and more from even experienced chemists.

Wiki also provides an alternate preparation:

"Laboratory methods
The above syntheses are useful but do not deliver NH2Cl in pure form. For research purposes, the pure compound can be prepared by contacting fluoroamine with calcium chloride:

NH2F + CaCl2 → NH2Cl + CaClF "

Now, here is a new untried and simple synthesis to NH2OH (translation: big ?). If someone is willing to undertake it, I think the results would be interesting, although I would ascribe a low chance of success. Basis, per Watt's Volume 4, page 471 (link http://books.google.com/books?id=FyzPAAAAMAAJ&pg=PA471&a... on the reaction of moist Silver oxide to quote:

"—7. The moist oxide removes halogens from many halogen containing organic compounds, replacing the halogen by OH (e.g. 2NMe4I + Ag2O.H20 = 2NMe4OH + 2AgI)"

Here is another more recent reference (see http://www.bajpaigroup.com/study%20matrial/IC25.PDF ) using moist Ag2O or AgOH to form alcohols. Cited reaction:

R-CH2-X + AgOH (aq) --> R-CH2-OH + AgX

So the proposed reaction would be to add moist Ag2O to a small volume of dilute ethereal chloramine solution (as per this synthesis http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0408 ) or an aqueous chloramine solution.

Ag2O.H2O + 2 NH2Cl --?--> 2 NH2OH + 2 AgCl (s)

One concern is that the Ether (Et2O) and a Ag2O.H2O suspension may not produce a reaction as water and Silver oxide do not dissolve in ether. The aqueous synthesis would have to be treated with HCl to form a stable salt.


[Edited on 9-11-2012 by AJKOER]

AndersHoveland - 9-11-2012 at 21:55

I have had this thought also. One would naturally wonder whether the chlorine atom in chloramine could be substituted with a hydroxyl group. I think this would be theoretically possible, but the reaction is very problematic because there are other competing reactions, and any resulting hydroxylamine (being a reactive reducing agent) would tend to get immediately oxidized.

NH2Cl + H2O <==> NH3 + HOCl

NH2Cl + OH[-] <==> NH3 + OCl[-]

I am not entirely sure exactly how the N-Cl bond behave in nucleophilic substitution reactions. Usually with the hydrolysis of the N-Cl bond with water, it is the nitrogen atom takes the hydrogen atom, not the chlorine atom. But the other way may also be possible.

I believe this may be analogous to the reactions of haloalkanes with bases. Chloroalkanes generally do not react, while bromoalkanes are much more reactive, and iodoalkanes being even slightly more reactive. (DMSO is a good solvent for this reaction)

One investigation mentions that nucleophilic substitution on chloramine to form chloride ions proceeds at a rate more than 100 times that of chloromethane, which may still be rather slow. Consider for example that the hydrolysis of chloromethane with water takes around a whole year!
"Gas phase reactions of NH2Cl with anionic nucleophiles: nucleophilic substitution at neutral nitrogen", Roustam Gareyeva, Shuji Katoa, Veronica M. Bierbauma


Quote:

Anhydrous chloramine is an extremely hazardous (toxic and explosive) and unstable (decomposes at −50 °C) compound. Therefore, it was prepared in situ in an aqueous solution according to the modified Raschig method: Aqueous ammonia (30%) and a solution of sodium hypochlorite (11%–13% available chlorine), both chilled to −18 °C, were mixed in a 1:4 ratio by volume (a slight excess of hypochlorite) in an ice/NaCl bath. The resulting fresh solution of chloramine (10 mL, ≈3 M; kept in an ice/water bath at 0 °C) was immediately used for experiments.





The intermediate formation of hydroxylamine could potentially explain how some of the ammonia gets oxidized to nitrogen by alkaline solutions of hypochlorite.

NH3 + OCl[-] <==> NH2Cl + OH[-] --> NH2OH + Cl[-]

(2) NH2OH + OCl[-] --> H2O + N2 + Cl[-]

Again, chloramine itself acts as an oxidizing agent, and in fact aqueous solutions of chloramine are not entirely chemically stable, especially at higher concentrations. This should not really be surprising if we consider the equilibrium.

Unless there was some sort of protecting group on the hydroxylamine, it will get oxidized as quick as it forms. I am not sure, perhaps some sort of Raschig synthesis with gelatin would work, analogous to that for preparing hydrazine. Using something like (CH3)2C=N-Cl would probably not work either, because the resulting oxime could tautomerise to a nitroso group, which would then be first oxidized and then chlorinated to (CH3)2C(NO2)Cl

If you look at my previous post in this thread, you can see an idea for protecting groups that might work.

king9491 - 5-2-2015 at 06:42

how to produce hydroxylamine in lab??
;)



how to produce NH2OH

king9491 - 5-2-2015 at 06:43

I need the process and how to synthesis NH2OH in lab.

Loptr - 5-2-2015 at 07:01

You can buy it on eBay for cheap. I found a listing from ChemSavers that is pretty well priced, in my opinion. Then again, I have little use for it, and would only purchase around 100g, so it depends on how much you need.

Org. Synth. 1923, 3, 61
DOI: 10.15227/orgsyn.003.0061
HYDROXYLAMINE HYDROCHLORIDE and ACETOXIME

http://www.orgsyn.org/demo.aspx?prep=cv1p0318

You could always attempt to get it from overseas, but in general, it helps if you are associated with a legitimate business entity.

[Edited on 5-2-2015 by Loptr]

[Edited on 5-2-2015 by Loptr]

I did not notice the discussion above reagarding this topic. You need to at least attempt to do your own book work before making a request like this. I have easily found several procedures in under ten minutes, and I do not have any academic affiliations at this time.

[Edited on 5-2-2015 by Loptr]

Shivachemist - 5-2-2015 at 07:05

I'm going to take a video about hydroxylamine soon ( Sodium carbonate, Sodium nitrite and sulfur dioxide as starting materials)

Boffis - 5-2-2015 at 07:12

@ king9491 there are numerous references to the preparation of hydroxylamine and its salts on this site, in Bauer in the forum library and elsewhere, try UTFSE

Also are you looking for the salts or the free base in a suitable solvent or the anhydrous hydroxylamine? The latter is highly unstable.